Reactive dressings intended to render cellulose fabrics uncreasable



United States Patent 974,38 Us. or. 8116.3 11 Claims Int. Cl. D06xn13/38 ABSTRACT OF THE DISCLOSURE A process is disclosed for treatingcellulose fabrics with cyclic urea-formol resins to provide wash andwear fabrics which are resistant to chlorine degradation. This isaccomplished by utilizing with the dressing resin in a catalyst ofglyoxylic acid.

The present invention relates to the treatment of cellulose fabrics withknown resins, modified however by glyoxylic acid, and in particular toan improved method for rendering such fabrics still more uncreasable andto treatment with chlorine, especially washing followed by treatmentwith chlorine, especially washing with the socalled Javel water (anaqueous solution of sodium hypochlorite and sodium chloride).

It has already been proposed to render cellulose fabrics, particularlycotton, uncreasable by applying to them methylolated derivatives ofethylene-urea, mono-ureine of glyoxal, that is to say ofimidazolidinone-Z, and glycoluryl, and then causing the reaction ofthese different reactive dressings by the methylolated groups with thecellulose in order to etherify this latter.

These types of dressings belong to the group of the methylolatedderivatives which are difiicult to condense on themselves, but whichreact readily on the hydroxyl groups of cellulose. They result infabrics having good wash and wear characteristics, the value of whichcan only be determined by visual comparison of the fabrics afterWashing, with reference to types such as those proposed by theA.A.T.C.C. In fact, these qualities give the natural fibres the abilityto retain their shape during washing, rapidity of drying, uncreasingafter creasing, strength in the dry and Wet states and great resistanceto washing, while giving properties of good tensile strength, goodresistance to tearing and to abrasion.

The above-mentioned products belong to the group of cyclic-formol ureasand do actually give these general effects. Unfortunately, in countriesin which household linen and underwear are treated with Javel waterafter soaping, the resistance of the dressings to chlorine is the basisof their choice. It is known that apart from the methyloltriazinones,which although they absorb chlorine do not cause any appreciable attackduring the ironing of the dressed cellulose, the above-mentioned resinsgive rise to a very considerable degradation of the fabrics during thecourse of these operations.

A considerable amount of work has been carried out in laboratories inorder to determine the mechanism of the action of chlorine and that ofthe attack of cellulose during ironing. The factors have been discoveredwhich influence the stability to chlorine and the evolution of thelatter during the course of successive washings.

The fixation of the cellulose with the CH OH groups would be effected bythe formation of co-valent bonds with the elimination of water.Furthermore, the hypochlorous ion can be fixed like chlorine on thenitrogen of the methylolamides when the latter processes hydrogen atomsdirectly associated with nitrogen, to form chloramides.

The chloramides formed are stable during washing and can only bedestroyed by the action of a de-chlorinating product such as bisulphite,hydrogen peroxide, perborate.

The formation of these chloramides is indicated by the appearance of aslight odour of chlorine and a yellowish colour. They decompose underheat during ironing for example, liberating hydrochloric acid andnascent oxygen. The cellulose is degraded simultaneously by thehydrochloric acid and the nascent oxygen. This rapid degradation whilehot can also occur, but very slowly, by the action of light andmoisture.

In the case of methylolated cyclic ureas which no longer comprise CONHgroups capable of fixing chlorine following the reaction:

there is however observed a poor resistance to chlorine of the fabricstreated. This must be attributed to the fact that a cerain percentage ofCH OH groups have remained free and become hydrolised so as to re-formthe CONH groups, and these, when re-introduced on to the fibre, renderit sensitive to chlorine.

Catalysts such as tartaric, lactic, oxalic and glycolic acids, whilethey are suitable for uncreasable dressings containing dimethylol-urea,are not suitable for the methylolated cyclic ureas such asdimethylol-ethylene-urea.

It could therefore not be foreseen that glyoxylic acid should provesuitable for acting as a catalyst with the cyclic ureas.

Now, according to the present invention, the applicants have found thatglyoxylic acid is perfectly suitable as a catalyst with certain cyclicureas. Furthermore, even when applied alone, glyoxylic acid has anaction as an agent intended to give fabrics good uncreasability, whichfact has not been observed up to the present time.

The invention is characterized by the fact that glyoxylic acid, by itsnature as an acidic catalyst and by its aldehyde function which enablesit to become fixed on cellulose by causing a reticulation between thechains, gives certain methylolated cyclic ureas the possibility ofsupplying highly uncreasable fabrics which are resistant to the actinonof chlorine.

Without departing from the scope of the invention, it is possible to addto solutions containing glyoxylic acid and the methylolated derivative,a more or less considerable quantity of metallic salts currentlyemployed as condensation catalysts, such as: hexahydrated magnesiummagnesium chloride, hexahydrated zinc nitrate, etc.

Other agents employed in the industry of uncreasable fabrics, such assofteners, high vinyl, acrylic, etc., polymers, may be present in theimpregnating solution or may be added subsequently.

In order to obtain at the same time uncreasability and resistance tochlorine, it is essential that the ratio of the methylolated derivativeto glyoxylic acid is such that the glyoxylic acid present exercises asufiicient action on the condensation of the methylolated groups inorder that, at the end of the treatment, the latter have wholly enteredinto reaction.

In order to facilitate this complete reaction of the methylols which isessential in order that the resistance to chlorine may persist afterseveral washings, the function of the glyoxylic acid as a condensationcatalyst may be completed by other inorganic or organic catalysts.

The cyclic methylolated derivatives suitable for the method of theinvention are for example those which are particularly described in thepresent applicants French Patent No. 1,351,590 of Dec. 28, 1962.

Dimethylol dihydroxy-ethylene-urea also gives very improved performancesby catalysis with glyoxylic acid.

The amount of absorption by the wet fabric is regulated so that theincrease in weight is comprised between 2 and 20% or more, the optimumproportion being in general between 5 and 12%. The proportion ofglyoxylic acid based on the anhydrous product may vary from 1% to 100%by weight with respect to the dry methylolated derivative.

In the tests which follow, given by way of illustration and not in anyway restricting the present invention, the parts and percentages areindicated by Weight.

The tests of which the results are given in the examples were carriedout on the fabric treated which was kept at C. and a relative humidityof 65%. The tensile strength given in kgs., forms the subject of theFrench AFNOR specification G-07-001-44.

The resistance to chlorine (Scorch Test) is measured 20 in accordancewith the Tentative Test Method 92-195'8-t, adopted in 1961 by theA.A.T.C.C. (American Association of Textile Chemists and Colorists) Theflattening angle, after a wrong fold in the dry state,

following the method adopted by Monsanto, by reference to the samplecomprised in the Monsanto Three-Dimensional Standard, Tentative TestMethod kit, following the proposal of the A.A.T.C.C.

EXAMPLE 1 Utilizing a condensate of cyclic methylolated urea modified byacryl-amide prepared under the conditions defined in the French patentreferred to above, this is diluted until a solution is obtained having15 grams of dry product per litre. Impregnations were made by padding acotton fabric of the reinforced cretonne type, bleached 3232, 50-50, of132 grams per square metre.

Wringing rates of the order of 90% are employed. All the sample piecesare placed on a frame and dried at 90 C. for 10 minutes before beingcondensed for 5 minutes at 150 C. in a ventilated oven.

The results are given in Table I below. By way of comparison, theresults obtained with the usual catalysts, magnesium chloride, zincnitrate, are also shown.

In this table, and also in all the other tables which are given below,the values shown in parentheses represent the sum of the valuesindicated for Warp (Wp) on the one hand and Weft (Wt) on the other.

TABLE I Dynamo Unereasability W & W Monsanto test Scorch test Test Bathformula and working conditions Strength Whiteness A.A.T.C.C., percentN0. (kg.) As it is 2 Wash 2 wash 5 wash (as it is) Wp/W t Wp/W t Wp/WtAs it is 5 wash 354 Methylolated derivative (dry state), 15 g.; 29.8/301 133/132 139/ 3 81 33 MgClzfiHzO, 6.65. (59. 9) (265) (282) Dryingat 90 C. for 10 min. Condens. at 150 C. for 5 min.

294 Methylolated derivative (dry state), 15 g.; 29. 8/25. 4 145/129132/130 80. 5 2O ZnNOafiHzO, 2.25. (55. 2) (274 (262) Drying at 90 C.for 10 min. Condens. at 150 C. for 5 min. 457"--- Methylolatedderivative (dry state), 15 g.; 27. 3/30. 2 151/140 146/131 5 4. 66 81 3.25. 7

CHOCOOH, 6 65 (57. 5) (291) (277) Drying at 90 0'. for 10 min. Condens.at 150 C. for 5 min.

1 Not evaluated.

is the angle obtained with the apparatus of the I.T.F. (InstituteTextile de France), following the definition of the Societe pour laDiffusion dAppareils de Mesures et de Controles.

The washings are carried out in an automatic Washing machine of thedomestic type, with a solution of 30 grams per litre of block soap inflakes and 15 grams per litre of anhydrous sodium carbonate per litre oftap-water.

The operation is carried out up to boiling, the rinsing being effectedup to the evacuation of all the alkaline water.

The evaluation of the [wash and Wear, that is to say the appearance ofthe fabric after washing, is carried out best catalyst in respect ofuncreasability.

EXAMPLE 2 The same procedure is followed as in Example 1, but with 25grams per litre of methylolated product. The results are shown in TableII.

TABLE II Dynamo Unereasability W & W Monsanto test Scorch test Test Bathformula and working conditions Strength Whiteness A.A.T.O.G., percentNo. (kg) As it is 2 wash 2 wash 5 wash (as it is) Wp/Wt Wp/Wt Wp/Wt Asit is 5 wash 357. Methylolated derivative (dry state), 25 g.; 28. 3/26.2 132/137 141/137 4. 5 5 81 17. 5

MgClzGHgO, 3.75. (54. 5) (269) (278) Drying at C. for 10 min. Condens.at 150 C. for 5 min.

303..." Methylolated derivative (dry state), 25 g.; 30. 6/32. 4 /135118/118 81 73 Z11(NO3)26H2O 3.75. (63) (270) (236) Drying at 90 C. for10 mm. Condens. at C. for 5 min.

306..-" Methylolated derivative (dry state), 25 g.; 21. 9/22. 5 138/147133/131 82. 5 -7 Zn(N( )a)z6H1O 7.5. (44. 4) (285) (264) Dryung at 90 C.for 10 111111. Condens. at 150 C. for 5 min.

460---" Methylolated derivative (dry state), 25 g.; 29. 2/25. 8 146/138135/145 5 5 81 3. 28 9 OHOCOOH, 11 25 (55) (284) (280) 6 Drying at 90 (lfor 10 min. Condens. at 150 C. for 5 min.

1 Not evaluated.

EXAMPLE 3 The same procedure is followed as for Example 1, but with 50grams per litre of the methylolated product. The results are shown inTable III.

TABLE III Dynamo Uncreasabilit W & W Monsant t Test Bath formula andworking conditions Strength y est Whiteness A.A.? f C C l g rcent No. (kAs it is 2 Wash 2 wash wash (as it is) Wp/Wt Wp/Wt Wp/Wt As it is 5 wash378".-. Methylolated derivative (dry state) 50 g. 22. 4/20. 1 144/147134/143 4 4. 5 81 zfi z y (42, 5) 291 (277) 67 Drying at 90 C. for 10min. Condens. at 150 C. for 5 min.

321 Methylolated derivative (dry state) 50 g: 23. 4/21. 1 148/149139/145 4. 4. 79

Drying at 90 C. for 10 111111. Condens. at 150 C. for 5 min.

463"--- Methylolated derivative (dry state) g." 22. 9/20. 5 152/154 142138 5 5 2.

Drying at 90 C. for 10 min. Condens. at 150 C. for 5min.

EXAMPLE 4 The same procedure is followed as for Example 1, but withgrams per litre of methylolated product. The results are shown in TableIV.

TABLE IV Dynamo Uncreasabilit W & W \Ionsa t t t Test Bath formula andworking conditions Stren th 4 y l n 0 es whiteness g fg g N (kg. As itis 2 wash 2 wash 5 wash (as it is) Wp/W t Wp/Wt Wp/Wt As it is 5 wash384--- Methylolated derivative (dry state) 75 g.- 21. 9/19. 2 146/149144/142 5 5 32 2 Drying at 90 C. for 10 min. Condens. at 150 C. for 5min.

330 Methylolated derivative (dry state), 75 g.; 20. 7/18. 5 150/146150/148 5 5 81 0 Z11(NO3)26H20, 11.25. (39 2 (296) (298) Drying at 90 C.for 10 min. Condens. at 150 C. for 5 min.

466. Methylolated derivative (dry state) 75 g. 23. 8/22. 9 160/155144/150 5 5 1, 5

Drying at 90 C. for 10 min. Condens. at 150 C. for 5 min.

EXAMPLE 5 As the impregnation solution, there was utilized a solution of25 grams per litre of a cyclic urea-formol condensation product(prepared by condensing simultaneously 1 mol of glyoxal, 2 mols offormaldehyde and 1 mo] 45 of urea). The results are shown in Table V.

TABLE V Dynamo Unereasability W & W Monsanto test Scorch test Test Bathformula and working conditions Strength whiteness A.A.T.C.C., percentNo. (kg) As it is 2 wash 2 Wash 5 wash (as it is) Wp/Wt. Wp/W t Wp/W tAs it is 5 wash 411(a) Methylolated derivative (dry state), 25 g.; 23.6/33. 2 139/135 133/139 4 32 74 Zn(NO:):6HzO, 7.5 g. (46. 8) (274) (272)Drying at C. for 10 min. Condens. at C. for 5 min.

536 Methylolated derivative (dry state), 25 g.; 25. 5/24 136/135 127/1304. 75 4. 5 82 5. 6 4 1 CHOCOOH, 12.5 g. (49. 5) (271) (257) Drying at 90C. for 10 min. Condens. at 150 C. for 5 min.

EXAMPLE 6 0 The same dressing solution was applied as in Example 5, butwith a concentration of 75%. The results are shown in Table VI.

TABLE VI Dynamo Uncreasability W & W Monsanto test Scorch test Test Bathformula and working conditions Strength whiteness A.A.T.C C., percent0:7), As it is 2 wash 2 wash 5 wash (as it is) Wp Wp/Wt Wp/Wt As it is 5wash 417 Methylolatedderivative (dry state), 75 g.; 18/15. 3 146/149144/144 4. 5 79 7.2 58

Z1'1(N03)n6HzO, 22.5 g. (33. 3) (295) (288) Drying at 90 C. for 10 min.Condens. at 150 C. for 5 min.

538 Methylolated derivative (dry state), 75 g.; 19. 9/ 18 139/ 147149/143 4. 75 4. 75 82 0 0 CHOCOOH 37.5 g. (37. 9) (286) (292) Drying at50" o. for 10 min. Condens. at 150 C. for 5 min.

7 EXAMPLE 7 A solution of dimethylol glyoxal mono-ureine is employed atdifferent concentrations. The results are given in Table VII.

impregnating bath consisting essentially of an aqueous solution ofglyoxylic acid and at least one reactive dressing resin containingmethylol groups and capable of reacting with the hydroxyl groups presentin the cellulose TABLE 'VII Dynamo Uncreasability W & W Monsanto testScorch test Test Bath formula and working conditions Strength whitenessA.A.'I.C.C., percent N 0. kg.) As it is 2 wash 2 wash 5 wash (as it is)Wp/Wt Wp/Wt Wp/W t As it is 5 wash 548"". Methylolated derivative (drystate), 25 g.; 25. 7/26. 6 127/130 118/137 4. 25 83 12. 8 21 CHOCOOH,12.5 g. (52. 3) (257) (255) Drying for 10 min. Condens. for 5 min.

550 Methylolated derivative (dry state), 75 g.; 19. 4/15. 5 143/140125/127 4. 75 82 2. 6 l7. 6

CH COOH, 37.5 g. (34. 9) (283) (252) Drying for 10 min. Condens. formin.

EXAMPLE 8 In this example, glyoxylic acid alone Was employed as theanti-creasing agent. The results are shown in Table VIII.

and selected from the group of the cyclic urea-formol resins, theproportion of glyoXylic acid with respect to said dressing being in apercentage comprised between 33 and 50%; squeezing out the aqueoussolution in TABLE VIII Dynamo Uncreasability W & W Monsanto test Scorchtest Test Bath formula and Working conditions Stren th WhitenessA.A.I.C.C., percent No. (kg. As it is 2 wash 2 wash 5 wash (as it is)Wp/W t Wp/Wt Wp/Wt As it is 5 wash 501 7.5 grams per litre of CHOOOO H.27/23. 5 107/118 107/100 4. 5 82. 5 +0. 3 7

Drying at 90 C. for min. (50. 5) (225) (207) Condens. at 150 C. for 5min.

502.-. 12.5 grams per litre of CHOCOOH. 25. 1/24. 1 121/125 100/112 4. 582. 5 --2 5. 2

Drying at 90 C. for 10 min. (49. 2) (246) (212) Condens. at 150 C. for 5min.

04... 37.5 grams per litre of CHOCOOH. 19. 4/19. 5 130/148 114/117 5 83-2. 1 -8. 7

Drying at 90 C. for 10 min. (38. 9) (278) (231) Condens. at 150 C. for 5min.

We claim:

1. A method of treatment of a fabric of cellulose tfiber, comprising thesteps of: immersing said fabric in an impregnating bath constituted byan aqueous solution comprising at least glyoxylic acid having aconcentration of about 7.5 to 37.5 grams of glyoxylic acid per litre ofsaid solution; squeezing out the aqueous solution in such manner thatthe increase in weight of such fabric is comprised between 2 to andmore; drying for about 10 minutes at about 90 C. and subjecting saidfabric to a thermal operation for about 5 minutes at about 150 C.

2. A method of treatment of a fabric of cellulose fibre comprising thesteps of: immersing said fabric in an impregnating bath consistingessentially of an aqueous solution of glyoxylic acid and at least onereactive dressing resin totally methylolated and capable of reactingwith the hydroxyl groups present in the cellulose and selected from thegroup of the cyclic urea-formol resins, the proportion of glyoxylic acidwith respect to said dressing being in a percentage from 10% to 100%;squeezing out the aqueous solution in such manner that the increase inweight of said fabric is comprised between 2 ot 20% and more; drying andsubjecting said fabric to a thermal operation.

3. A method of treatment of a fabric of cellulose tfibre comprising thesteps of: immersing said fabric in an impregnating bath consistingessentially of an aqueous solution of glyoxylic acid and at least onereactive dressing resin containing methylol groups and capable ofreacting with the hydroxyl groups present in the cellulose and selectedfrom the group of the cyclic urea-formol resins, the proportionofglyoxylic acid with respect to said dressing being in a percentagevarying from 10% to 100%; squeezing out the aqueous solution in suchmanner that the increase in weight of said fabric is comprised between 5and 12%; drying and subjecting said fabric to a thermal operation.

4. A method of treatment of a fabric of cellulose fibre, comprising thesteps of: immersing said fabric in an such manner that the increase inweight of said fabric is comprised between 2 and 20% and more; dryingand subjecting said fabric to a thermal operation.

5. A method of treatment of a fabric of cellulose fibre, comprising thesteps of: immersing said fabric in an impregnating bath consistingessentially of an aqueous solution of glyoxylic acid and at least onereactive dressing resin containing methylol groups and capable ofreacting with the hydroxyl groups present in the cellulose and selectedfrom the group of the cyclic urea-formol resins, the proportion ofglyoxylic acid with respect to said dressing being in a percentagevarying from 33 to 50%; squeezing out the aqueous solution in suchmatter that the increase in weight of said fabric is comprised between 5and 12%; drying and subjecting said fabric to a thermal operation.

6. A method of treatment of a fabric of cellulose fibre, comprising thesteps of: immersing said fabric in an impregnating bath constituted byan aqueous solution comprising at least glyoxylic acid; squeezing outthe aqueous solution in such manner that the increase in weight of saidfabric is comprised between 2 and 20% and more; drying and subjectingsaid fabric to a thermal operation carried out at a temperature of to180 C. for a period of from one minute to one hour.

7. A method of treatment of a fabric of cellulose fibre, comprising thesteps of: immersing said fabric in an impregnating bath constituted byan aqueous solution comprising at least glyoxylic acid; squeezing outthe aqueous solution in such manner that the increase in weight of saidfabric is comprised between 2 and 20% and more; drying and subjectingsaid fabric to a thermal operation carried out at C. for 5 minutes.

8. A method of treatment of a fabric of cellulose fibre, comprising thesteps of: immersing said fabric in an impregnating bath consistingessentially of an aqueous solution of glyoxylic acid and at least onereactive resin dressing containing methylol groups and capable ofreacting with the hydroxyl groups present in the cellulose and selectedfrom the group of the cyclic ureaformol resins, the proportion ofglyoxlic acid with respect to said resin dressing being in a percentagecomprised between and 100%; squeezing out the aqueous solution in suchmanner that the increase in weight of said fabric is comprised between 2and and more; drying and subjecting said fabric to a thermal operationcarried out at a temperature of 130 to 180 C. for a period of from oneminute to one hour.

9. A method of treatment of a fabric of cellulose fibre, comprising thesteps of: immersing said fabric in an impregnating bath consistingessentially of an aqueous solution of glyoxylic acid and at least onereactive resin dressing containing methylol groups and capable ofreacting with the hydroxyl groups present in the cellulose and selectedfrom the group of the cyclic ureaformol resins, the proportion ofglyoxylic acid with respect to said dressing being in a percentagecomprised between 10 to 100%; squeezing out the aqueous solution in suchmanner that the increase in weight of the fabric is comprised between 5and 12%; drying and subjecting said fabric to a thermal operationcarried out at a temperature of 130 to 180 C. for a period of from oneminute to one hour.

10. A method of treatment of a fabric of cellulose fibre, comprising thesteps of: immersing said fabric in an impregnating bath consistingessentially of an aqueous solution of :glyoxylic acid and at least onereactive resin dressing containing methylol groups and capable ofreacting with the hydroxyl groups present in the cellulose and selectedfrom the group of the cyclic ureaformol resins, the proportion ofglyoxylic acid with respect to said dressing being in a percentagecomprised between 33 and squeezing out the aqueous solution in suchmanner that the increase in weight of the fabric is comprised between 2and 20% and more; drying and subjecting said fabric to a thermaloperation carried out at a temperature of to C. for a period of from oneminute to one hour.

11. A method of treatment of a fabric of cellulose fibre, comprising thesteps of: immersing said fabric in an impregnating bath consistingessentially of an aqueous solution of glyoxylic acid and at least onereactive resin dressing containing methylol groups and capable ofreacting with the hydroxyl groups present in the cellulose and selectedfrom the group of the cyclic ureaformol resins, the proportion ofglyoxylic acid with respect to said dressing being in a percentagecomprised between 33 and 50%; squeezing out the aqueous solution in suchmanner that the increase in weight of said fabric is comprised between 5and 12%; drying and subjecting said fabric to a thermal operationcarried out at a temperature of 130 to 180 C. for a period of from oneminute to one hour.

References Cited UNITED STATES PATENTS 2,898,238 8/1959 Van Loo et a1.

NORMAN G. TORCHI-N, Primary Examiner I. P. BRAMMER, Assistant ExaminerUS. Cl. X.R. 81 16, 116.2

